The general field of nanotechnology has long been a subject of speculation (Drexler, K. E. Nanosystems. Molecular Machinery, Manufacturing, and Computation; John Wiley & Sons, Inc.: New York, 1992) and much progress in the experimental design of two-and three-dimensionally networked three-dimensional crystal structures and supramolecular architecture has been reported. (Wang, X., Simard, M., Wuest, J. D., J. Am. Chem. Soc. 1994, 116, 12119; Wu, Z., Lee, S., Zhang, J., Pesak, D. J., Ludwick, J. L., Moore, J. S., J. Am. Chem. Soc. 1994, 116, 4227; Chen, J., Seeman, N. Nature 1991, 350, 631; Abrahams, B. F., Hoskins, B. F., Michail, D. M., Robson, R., Nature 1994, 369, 727; Fagan, P. J., Ward, M. D., Calabrese, J. C., J. Am. Chem. Soc. 1989, 111, 1698; Stein, A., Keller, S. W., Mallouk, T. E., Science 1993, 259, 1558; Yaghi, O. M., Li, H., J. Am. Chem. Soc. 1995, 117, 10401; MacGillivray, L. R., Subramanian, S., Zaworotko, M. J., J. Chem. Soc. Chem. Commun. 1994, 1325; Gardner, G. B., Venkataraman, D., Moore, J. S., Lee, S., Nature 1995, 374, 792; Bein, T.,Ed. Supramolecular Architecture: Synthetic Control in Thin Films and Solids, American Chemical Society: Washington, D.C., 1992; Michl, J., Ed. Modular Chemistry, Kluwer: Dordrecht, The Netherlands, in press; Kohnke, F. H., Mathias, J. P., Stoddart, J. F., Angew. Chem., Int. Ed. Engl. 1989, 28, 1103; Lehn, J.-M. Angew. Chem., Tnt. Ed. Engl. 1990, 29, 1304; Lehn, J.-M. Supramolecular Chemistry, VCH Publishers: Weinheim, 1995.) However, crystal engineering and self-assembly by weak interactions are only indirectly related to the methods of the present invention.
The ultimate goal of the methods of this invention is the construction or fabrication of molecular-sized structures (e.g., nets, grids or the like) by controlled combination of elementary modules (e.g., monomers) to form large structurally-defined molecules (e.g., polymers). The modules and methods employed for construction of such structures are reminiscent of children's "TINKERTOY" (Trademark, Playskool, Inc., Pawtucket, R.I.) construction kits. The elementary modules used in the methods of this invention preferably comprise molecular rods and connectors. The general use of such molecular elements for molecular construction has been described in the review article: J. Michl 1995 "The `Molecular Tinkertoy` Approach to Materials" in Proceedings of the NATO ARW Meeting: Applications of Organometallic Chemistry in Preparation and Processing of Advanced Materials Cap d'Agde, France, Sepptember 1994 (J. Harrod, ed.) Kluwer, Dordrecht, Netherlands, which is incorporated in its entirety by reference herein. U.S. Pat. No. 5,405,550 (J. Michl et al.), which is also incorporated by reference in its entirety herein, gives a general description of the molecular "Tinkertoy" construction system, various molecular structures that can be made using the system, exemplary connector and rod components of such systems, exemplary chemistry of coupling rods to connectors and specific examples of the use of 1.1.1!propellanes as rod components.